CN102089717B - Charge controlling agent and toner using metal compound of cyclic phenol sulfide - Google Patents

Charge controlling agent and toner using metal compound of cyclic phenol sulfide Download PDF

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Publication number
CN102089717B
CN102089717B CN200980126718.2A CN200980126718A CN102089717B CN 102089717 B CN102089717 B CN 102089717B CN 200980126718 A CN200980126718 A CN 200980126718A CN 102089717 B CN102089717 B CN 102089717B
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toner
acid
phenol sulfide
cyclic phenol
metallic compound
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CN102089717A (en
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安村正照
伊藤雅美
青木良和
大久保正树
大塚英之
渡边纯
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Hodogaya Chemical Co Ltd
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Hodogaya Chemical Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/097—Plasticisers; Charge controlling agents
    • G03G9/09783—Organo-metallic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/097—Plasticisers; Charge controlling agents
    • G03G9/09733—Organic compounds
    • G03G9/0975—Organic compounds anionic
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/097—Plasticisers; Charge controlling agents
    • G03G9/09733—Organic compounds
    • G03G9/09775—Organic compounds containing atoms other than carbon, hydrogen or oxygen

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  • General Physics & Mathematics (AREA)
  • Developing Agents For Electrophotography (AREA)

Abstract

Provided are a charge controlling agent comprising, as the active ingredient, a metal compound of a cyclic phenol sulfide represented by the general formula (1) (wherein at least one of a plural number of Y's is a metal atom), and a toner comprising at least one kind of the above-described compound together with a coloring agent and a binder resin. This charge controlling agent overcomes the problems of less clearness in the early printed images and fluctuation in printed image qualities during continuous printing, shows a good charge rise which makes it applicable to high-speed printers employed in recent years, has an excellent environmental stability with little change in charge amount depending on a change in temperature or humidity, and has a large frictional charge amount. By using this charge controlling agent, a negatively charged toner having a high charge performance can be provided.

Description

Use charge control agent and the toner of the metallic compound of cyclic phenol sulfide
Technical field
The fields such as electronic photo, electrostatic recording that the present invention relates to are used for making the charge control agent that the image processing system of latent electrostatic image developing uses and the electronegative property toner that contains charge control agent.
Background technology
In the image forming course that adopts the electronic photo mode, at the inorganic photoreceptor such as selenium, selenium alloy, cadmium sulfide, amorphous silicon or use on the Organophotoreceptor of charge generating and charge transport agent and form electrostatic latent image, make it to develop with toner, be transferred on paper or plastic foil, photographic fixing obtains visual image.
Photoreceptor has positively charged and electronegative property according to its formation, stay in the situation of printing portion as electrostatic latent image by exposure, adopt the electrical toner development of band contrary sign, and printing portion is carried out in the situation of discharged-area development except after electricity, adopt the electrical toner development of band same-sign.Toner is made of adhesive resin and colorant and other adjuvants, in order to give desirable triboelectric characteristic (charged speed, charged level, band electrical stability etc.), ageing stability, environmental stability, generally uses charge control agent.Due to this charge control agent, the characteristic of toner is greatly affected.
In the past, the charge control agent of using as electronegative property, the Monoazo metal complex compound has been proposed (for example, with reference to patent documentation 1～2), the metallic complex salt compound of hydroxybenzoic acid derivative (for example, with reference to patent documentation 3～4), the aromatic dicarboxylic acid metal salt compound (for example, with reference to patent documentation 5), cup (n) aromatic compound (calyx(n) arene) (for example, with reference to patent documentation 6～8) and the scheme of the multiple compounds such as cyclic phenol sulfide (for example, with reference to patent documentation 9～11).
But, it is insufficient that these charge control agent great majority are given effect to the compatibility of the binding resin of toner and frictional electrification, charged commencing speed is slow, therefore exists the copy image at initial stage to lack distinctiveness, the shortcoming that when duplicating continuously, the quality of copy image easily changes.In addition, also exist the charged characteristic of toner large with respect to the amplitude of fluctuation of environmental baseline, the shortcoming of marked change can occur due to the seasonal factor image quality.
In recent years, used the Printers and Faxes machine of xerography and popularized, the speed of duplicating is accelerated year by year, more needs moment to keep the suitably toner of charged (electricity rises good) than former duplicating machine.That is to say, more need to be when dormant state enters output state than former toner moment keep suitably charged, even triboelectric behavior can be not deteriorated yet under the long-time state of placing.
Patent documentation 1: No. 3986488 communique of patent
Patent documentation 2: JP 2005-266790 communique
Patent documentation 3: JP 61-069073 communique
Patent documentation 4: No. 4056738 communique of patent
Patent documentation 5: JP 57-111541 communique
Patent documentation 6: No. 2568675 communique of patent
Patent documentation 7: No. 2899038 communique of patent
Patent documentation 8: No. 3359657 communique of patent
Patent documentation 9: JP 2003-295522 communique
Patent documentation 10:WO2007-111346 communique
Patent documentation 11:WO2007-119797 communique.
Summary of the invention
Target of the present invention is that the copy image that overcomes the initial stage lacks distinctiveness, the shortcoming that when duplicating continuously, the quality of copy image easily changes, its purpose is to provide a kind of can adapt to the high speed of printer in recent years, electricity rises good, variation with respect to the variation carried charge of temperature and humidity is little, environmental stability is good, the New Charge controlling agent that the friction belt electric weight is high.
The present invention also aims to provide the Novel belt electronegativity toner with highly charged performance that uses this charge control agent.
The present invention concentrates one's attention on to study the result that obtains for achieving the above object, mainly comprises following content.
1. a charge control agent, is characterized in that, contains the metallic compound of cyclic phenol sulfide of following general formula (1) expression as effective constituent.
[changing 1]
Figure 799328DEST_PATH_IMAGE001
(in formula, R represents straight chain shape or the alkyl of a chain, the ring type alkyl of carbon number 3 to 8, the straight chain shape of carbon number 2 to 6 or unsaturated alkyl or replacement or the unsubstituted aromatic hydrocarbyl of a chain of carbon number 1 to 6, Y represents hydrogen atom or metallic atom, m represents 4 to 9 integer, and n represents 0 or 1 to 2 integer.Wherein, in a plurality of Y at least 1 be metallic atom.）。
2. a toner, is characterized in that, contain in the metallic compound of cyclic phenol sulfide of above-mentioned general formula (1) expression more than a kind and colorant and binding resin.
The metallic compound of cyclic phenol sulfide of the present invention is the good compound of environmental stability, and is with the good compound of electric control effect.Be used for toner by the metallic compound with cyclic phenol sulfide of the present invention, can realize that electricity rises soon and carried charge is high, result can obtain distinct image.Therefore, the toner of using as high-speed printer (HSP) is suitable especially.
Charge control agent of the present invention is good aspect electric charge control characteristic, environment resistant and permanance, when being used for toner, can obtain not having photographic fog, image color, some repeatability, the good image of line reproducibility.
Even it is also less to contain the variation of toner charged characteristic under high humidity or low wet environment of metallic compound of cyclic phenol sulfide of the present invention, can keep stable developing property.
Contain the metallic compound of cyclic phenol sulfide of the present invention as the charge control agent of effective constituent, compare with charge control agent in the past, have charged commencing speed fast, the high-band electric weight is arranged, and the good charged characteristic of environmental stability.And the stability of dispersed and compound is also very good.
Embodiment
Use the charge control agent of the metallic compound of cyclic phenol sulfide of the present invention, can use separately that in above-mentioned general formula (1), each intramolecular n can be the same or different, n is the metallic compound of the cyclic phenol sulfide of 0 or 1 to 2 integer, also can mix use more than 2 kinds.
In addition, can use separately m in above-mentioned general formula (1) is the metallic compound of the cyclic phenol sulfide of 4 to 9 integer, also can mix use more than 2 kinds.
The straight chain shape of the carbon number 1 to 6 that represents as R in general formula (1) or the alkyl of a chain specifically can exemplify following radicals.Methyl, ethyl, n-pro-pyl, 2-propyl group, normal-butyl, sec-butyl, 2-methyl-propyl, the tert-butyl group, n-pentyl, 1-methyl butyl, 1-ethyl propyl, n-hexyl, 1-methyl amyl, 1-ethyl-butyl, 1-Ethyl-2-Methyl propyl group, 1,1,2-trimethyl propyl group.The wherein alkyl of the straight chain shape of preferred carbon number 1 to 4 or a chain, the particularly preferably tert-butyl group.
The straight chain shape of the carbon number 2 to 6 that represents as R in general formula (1) or the unsaturated alkyl of a chain specifically can exemplify following radicals.Vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl group, 2-pentenyl, 2-amylene-4-base, 1,3-butadiene base, ethinyl, 2-propynyl.The unsaturated alkyl of carbon number 2 to 4 particularly preferably wherein.
The ring type alkyl of the carbon number 3 to 8 that represents as R in general formula (1) specifically can exemplify following radicals.Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, 2-cyclopentene-1-base, 2-cyclohexene-1-base, 2,4-cyclopentadiene-1-base, 2,4-cyclohexadiene-1-base.The ring type alkyl of carbon number 3 to 6 particularly preferably wherein.
The replacement that represents as R in general formula (1) or the aromatic hydrocarbyl in unsubstituted aromatic hydrocarbyl specifically can exemplify following radicals.Phenyl, naphthyl, anthryl, fluorenyl, phenanthryl, indenyl, pyrenyl, styryl.
The replacement that represents as R in general formula (1) or the substituting group in unsubstituted aromatic hydrocarbyl specifically can exemplify the straight chain shape of fluorine atom, chlorine atom, trifluoromethyl, carbon number 1 to 4 or the alkyl of a chain.
As the metallic atom that Y in general formula (1) represents, can be all metals, preferred transition metal and earth alkali metal.As instantiation, can exemplify iron, cobalt, nickel, copper, zinc, titanium, vanadium, chromium, manganese, magnesium, calcium, strontium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, barium, tantalum, tungsten, rhenium, platinum, gold.Wherein preferred iron, cobalt, nickel, copper, zinc, titanium, magnesium, calcium and zirconium, particularly preferably iron, cobalt, nickel and zinc.
In the present invention, preferably making Y in every 1 mole of general formula (1) is that the polymkeric substance metallizing thing (metal imparting agent) of hydrogen reacts, make this metal approximately 1 mole react, prepare.Particularly preferably a plurality of Y shapes become the combination of metallic atom and hydrogen atom.
Raw material for the preparation of the metallic compound of cyclic phenol sulfide of the present invention, it is cyclic phenol sulfide, can prepare according to known method (for example, with reference to patent documentation 9～11, Unexamined Patent 10-081680 communique and WO1998-009959 communique).
The metallic compound of cyclic phenol sulfide of the present invention can be by the cyclic phenol sulfide as raw material, according to known method (for example, with reference to JP 2000-191658 communique and Tetrahedron, 57, p.5557(2001)) preparation.
The metal imparting agent that uses of metallic compound as preparation cyclic phenol sulfide of the present invention, can exemplify the slaines such as the halogenide of metal, the slaine of sulfuric acid, the slaine of nitric acid, the slaine of phosphoric acid, the slaine of acetic acid, the slaine of sulfonic acid, salicylic slaine, perhaps the metal complexs such as acetylacetonate complex, bipyridyl complexes, phenanthroline complex compound, ethylenediamine complex compound.
Charge control agent of the present invention uses after preferably volume average particle size being adjusted to 0.1～20 μ m, more preferably 0.1～10 μ m.If use the charge control agent of this particle size range, the amount of this charge control agent of toner surface appearance is suitable, can obtain good electric charge and control effect, and be reduced by the charge control agent that toner comes off, the problems such as machine intimate pollution can not appear, thus preferred.
Containing charge control agent of the present invention in toner as making---the method for the metallic compound of cyclic phenol sulfide has method (crushed toner) mixing after adding in binding resin, that pulverize together with colorant etc.; Perhaps add the method that makes it method (polymerization toner) that polymerization obtains toner etc. after the metallic compound of cyclic phenol sulfide and add in the inside of toner particle in advance (in add) in polymerizable monomer, and the method for making in advance and add at surfaces of toner particles after toner particle (outside add).As at toner particle is inner when adding charge control agent of the present invention---the addition of the metallic compound of cyclic phenol sulfide, with respect to binding resin 100 mass parts, be preferably 0.1～10 mass parts, more preferably 0.2～5 mass parts.In addition, when the outside interpolation of toner particle, with respect to binding resin 100 mass parts, be preferably 0.01～5 mass parts, more preferably 0.01～2 mass parts.In addition, preferably adopt the mechanochemistry method to make it to be fixed on surfaces of toner particles.
In addition, can unite use with the metallic compound of cyclic phenol sulfide of the present invention with other known electronegative property charge control agents as the charge control agent of effective constituent.As the preferred charge control agent of uniting use, can exemplify zirconium complex or the complex salt of the aluminium complex of the zinc complex of the chromium complex of azo iron complex or complex salt, azo chromium complex or complex salt, azo manganese complex or complex salt, azo cobalt complex or complex salt, azo zirconium complex or complex salt, carboxylic acid derivates or complex salt, carboxylic acid derivates or complex salt, carboxylic acid derivates or complex salt, carboxylic acid derivates.Above-mentioned carboxylic acid derivates optimization aromatic hydroxycarboxylic acid, more preferably 3,5-two-tert-butyl group salicylic acid.And, also can exemplify boron complex or complex salt, electronegative property resin type charge control agent etc.
Charge control agent of the present invention and other charge control agents are united addition when using preferably with respect to binding resin 100 mass parts, and other charge control agents beyond take the metallic compound of cyclic phenol sulfide of the present invention as the charge control agent of effective constituent are as 0.1～10 mass parts.
As the kind of the binding resin of the toner that uses in the present invention, so long as the known material of binding resin, all can use.Can exemplify the polyvinyl of styrene monomer, acrylic ester monomer, methyl acrylic ester monomer etc., the multipolymer that perhaps more than 2 kinds, these monomers consist of etc., polyester polymer, polyalcohols resin, phenolic resin, silicones, urethane resin, polyamide, furane resin, epoxy resin, xylene resin, terpene resin, coumarone indeneresin, polycarbonate resin, petroleum resinoid etc.
Styrene monomer, acrylic ester monomer, the methyl acrylic ester monomer that forms above-mentioned polyvinyl or multipolymer can exemplify as follows, but is not limited to this.
As styrene monomer, can exemplify styrene, o-methyl styrene, a methyl styrene, p-methylstyrene, to styryl phenyl, to ethyl styrene, 2, the 4-dimethyl styrene, to n-amylbenzene ethene, p-tert-butylstyrene, to positive hexyl phenenyl ethene, to n-octyl styrene, align nonyl benzene ethene, align decyl styrene, align dodecyl styrene, to methoxy styrene, to chlorostyrene, 3, the styrene or derivatives thereofs such as 4-dichlorostyrene, m-nitro ethene, ortho-nitrophenyl ethene, p-nitrophenyl ethene etc.
As acrylic ester monomer, can exemplified by acrylic or the acrylic acid such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid n-octyl, acrylic acid dodecyl ester, 2-EHA, stearyl acrylate base ester, acrylic acid 2-chloroethene ester, phenyl acrylate or its ester class etc.
As the methyl acrylic ester monomer, can exemplified by methyl acrylic acid, the methacrylic acid such as methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, n-BMA, isobutyl methacrylate, n octyl methacrylate, methacrylic acid dodecyl ester, 2-Ethylhexyl Methacrylate, methacrylic acid stearyl, phenyl methacrylate, dimethylaminoethyl methacrylate, diethyl aminoethyl methacrylate or its ester class etc.
Example as other monomers that form above-mentioned polyvinyl or multipolymer can exemplify following (1)～(18).(1) the monoene hydro carbons such as ethene, propylene, butylene, isobutylene; (2) polyenoid such as butadiene, isoprene class; (3) the vinyl halides classes such as vinyl chloride, vinylidene chloride, bromine ethene, fluorothene; (4) vinyl esters such as vinyl acetate, propionate, vinyl benzoate; (5) vinyl ethers such as vinyl methyl ether, EVE, vinyl isobutyl ether; (6) vinyl ketones such as ethenyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; (7) the N-vinyl compounds such as N-vinyl pyrrole, N-vinylcarbazole, N-vinyl indoles, NVP; (8) vinyl naphthalene class; (9) acrylic or methacrylic acid derivatives such as vinyl cyanide, methacrylonitrile, acrylamide etc.; (10) unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic, fumaric acid, mesaconic acid; (11) unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydrides; (12) monoesters of the unsaturated dibasic acids such as maleic acid one methyl esters, maleic acid one ethyl ester, maleic acid one butyl ester, citraconic acid one methyl esters, citraconic acid one ethyl ester, citraconic acid one butyl ester, methyl ester of itaconic acid, alkenyl succinic one methyl esters, fumaric acid one methyl esters, mesaconic acid one methyl esters; (13) unsaturated dibasic acid such as dimethyl maleate, dimethyl fumarate ester; (14) α such as butenoic acid, cinnamic acid, beta-unsaturated acid; (15) α such as crotonic anhydride, cinnamic anhydride, the beta-unsaturated acid acid anhydride; (16) this α, acid anhydrides, alkenyl malonic acid, alkenyl glutaric acid, alkenyl hexane diacid, these sour acid anhydrides and these the sour monoesters etc. that beta-unsaturated acid and lower fatty acid form have the monomer of carboxyl; (17) the acrylic or methacrylic acid hydroxyalkyl acrylates such as acrylic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, methacrylic acid 2-hydroxy propyl ester; (18) 4-(1-hydroxyl-1-methyl butyl) styrene, 4-(1-hydroxyl-1-methyl hexyl) styrene etc. has the monomer of hydroxyl.
In toner of the present invention, the polyvinyl of binding resin or multipolymer also can have by the crosslinked cross-linked structure that obtains of the crosslinking chemical that 2 above vinyl are arranged, the crosslinking chemical that uses in this case, as divinyl aromatic compound, can exemplify divinylbenzene, divinyl naphthalene.As the diacrylate compounds by the alkyl chain combination, can exemplify glycol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediyl ester, neopentylglycol diacrylate perhaps replace with the acrylate in above-claimed cpd the compound that methacrylate obtains.
Diacrylate compounds as the alkyl chain combination by containing ehter bond, can exemplify diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyglycol #400 diacrylate, polyglycol #600 diacrylate, propylene glycol diacrylate, perhaps the acrylate in above-claimed cpd be replaced with the compound that methacrylate obtains.
In addition, can also exemplify diacrylate ester compounds or dimethylacrylate compound by the chain combination that contains aromatic group and ehter bond.As polyester-type diacrylate class, can exemplify trade name MANDA(Nippon Kayaku K. K system).
As polyfunctional crosslinking chemical, can exemplify pentaerythritol triacrylate, trimethylolethane trimethacrylate acrylate, trimethylolpropane triacrylate, tetramethylol methane tetraacrylate, oligoesters acrylate and the acrylate in above-claimed cpd is replaced with compound, triallyl cyanurate, the trimellitic acid triallyl that methacrylate obtains.
These crosslinking chemicals can preferably use 0.01～10 mass parts with respect to other monomer component 100 mass parts, particularly preferably use 0.03～5 mass parts.In these cross-linkable monomers, be applicable to the material of resin for toner as the angle from tack, anti-offset printing (offset) property, can exemplify the diacrylate compounds of divinyl aromatic compound (particularly preferably divinylbenzene), the marriage chain combination by containing aromatic group and 1 ehter bond.Wherein, be preferably formed the combination of the monomer of styrene copolymer, cinnamic acrylic ester analog copolymer.
as the polymerization initiator for the preparation of polyvinyl of the present invention or multipolymer, can exemplify 2,2 '-azoisobutyronitrile, 2,2 '-azo two (4-methoxyl-2,4-methyl pentane nitrile), 2,2 '-azo two (2,4-methyl pentane nitrile), 2,2 '-azo two (2-methylbutyronitrile), dimethyl-2,2 '-azo-bis-isobutyrate, 1,1 '-azo two (1-cyclohexane formonitrile HCN), 2-(carbamyl azo)-isobutyronotrile, 2,2 '-azo two (2,4,4-trimethylpentane), 2-phenylazo-2 ', 4 '-dimethyl-4 '-methoxyl valeronitrile, 2,2 '-azo two (2-methylpropane), methyl-ethyl-ketone peroxide, acetylacetone peroxide, the ketone peroxide classes such as Cyclohexanone peroxides, 2,2-two (t-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethyl butyl hydroperoxide, di-t-butyl peroxide, tert-butyl group cumyl peroxide, dicumyl peroxide, α-(t-butylperoxy) cumene, the peroxidating isobutyl, the peroxidating decoyl, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethyl acetyl base superoxide, benzoyl peroxide, tolyl between peroxidating, di-isopropyl peroxydicarbonate, peroxy dicarbonate two-2-Octyl Nitrite, the peroxy dicarbonate di-n-propyl ester, peroxidating carbonic acid two-2-ethoxy ethyl ester, peroxy dicarbonate diethoxy isopropyl ester, peroxidating carbonic acid two (3-methyl-3-methoxyl butyl) ester, acetyl group cyclohexyl sulfonyl-peroxide, peroxide acetic acid butyl ester, the peroxidating tert-butyl isobutyrate, the peroxidating 2 ethyl hexanoic acid tert-butyl ester, the peroxidating lauric acid tert-butyl ester, the oxybenzene t-butyl formate, tert-butylperoxy isopropyl carbonate, peroxidating m-phthalic acid di tert butyl carbonate, peroxidating allylic carbon tert-butyl acrylate, peroxidating 2 ethyl hexanoic acid isopentyl ester, peroxidating six hydrogen terephthalic acid (TPA) di tert butyl carbonates, the peroxidating azelaic acid tert-butyl ester etc.
Binding resin is in the resinoid situation of cinnamic acrylic ester, in the molecular weight distribution that the composition that dissolves in tetrahydrofuran (being designated hereinafter simply as THF) in resinous principle records by gel permeation chromatography (being designated hereinafter simply as GPC), there is at least 1 peak in the zone of (converting by number-average molecular weight) in molecular weight 3,000～50,000, and there is the resin at least 1 peak in the zone at molecular weight more than 100,000, in tack, offset printing, preferred aspect conservatory.In addition, also preferably dissolving in molecular weight distribution in the composition of THF is 50～90% binding resin at the composition below 100,000.More preferably in the zone of molecular weight 5,000～30,000, most preferably has main peak in 5,000～20,000 zone.
Binding resin is that the acid number of the polyvinyl such as cinnamic acrylic ester resinoid is preferably 0.1mgKOH/g～100mgKOH/g, more preferably 0.1mgKOH/g～70mgKOH/g, further preferred 0.1mgKOH/g～50mgKOH/g.
Monomer as consisting of polyester polymer can exemplify following material.As glycol component, can exemplify ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2,3-butylene glycol, diglycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1, glycol that the cyclic ether such as 3-hexanediol, hydrogenated bisphenol A or oxirane, epoxypropane and bisphenol-A polymerization obtain etc.
In order to make vibrin crosslinked, preferably use simultaneously the above alcohol of ternary.As the polyvalent alcohol more than ternary, can exemplify sorbierite, 1,2, the own tetrol of 3,6-, Isosorbide-5-Nitrae-sorbitan, pentaerythrite, dipentaerythritol, tripentaerythritol, 1,2,4-butantriol, 1,2,5-penta triol, glycerine, 2-methyl-prop triol, 2-methyl isophthalic acid, 2,4-butantriol, trimethylolethane, trimethylolpropane, phloroglucinol etc.
As the sour composition that forms above-mentioned polyester polymer, can exemplify Phthalic acids or its acid anhydrides such as phthalic acid, m-phthalic acid, terephthalic acid (TPA), alkyl dicarboxylic aid or its acid anhydrides such as succinic acid, hexane diacid, decanedioic acid, azelaic acid, the unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic, fumaric acid, mesaconic acid, the unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydrides etc.In addition, as the polybasic carboxylic acid composition more than ternary, can exemplify trihemellitic acid, pyromellitic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butane tricarboxylic acid, 1,2,5-hexane tricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylene carboxyl propane, four (methylene carboxyl) methane, 1,2,7,8-octane tetracarboxylic acid, the acid of empol triploid or these sour acid anhydrides, part lower alkyl esters etc.
Binding resin is in the situation of polyester resin, dissolve in resinous principle in the molecular weight distribution of composition of THF, be the resin that there is at least 1 peak in 3,000～50,000 zone at molecular weight, preferred aspect the tack of toner, anti-offset printing, in addition, also preferably dissolving in molecular weight in the composition of THF is 60～100% binding resin at the composition below 100,000.More preferably there is at least 1 peak in the zone of molecular weight 5,000～20,000.
Binding resin is in the situation of vibrin, and its acid number is preferably 0.1mgKOH/g～100mgKOH/g, more preferably 0.1mgKOH/g～70mgKOH/g, further preferred 0.1mgKOH/g～50mgKOH/g.
In the present invention, the molecular weight distribution of binding resin is by measuring as the GPC of solvent with THF.
As the binding resin that can be used for toner of the present invention, also can use contain in above-mentioned polyvinyl composition and/or polyester resin composition can with the resin of the monomer component of these two kinds of resinous principles reactions.Consist of in the monomer of polyester resin composition, as can with the material of polyvinyl reaction, can exemplify the unsaturated dicarboxylic such as phthalic acid, maleic acid, citraconic acid, itaconic acid or its acid anhydrides etc.Monomer as consisting of the polyvinyl composition can exemplify the material with carboxyl or hydroxyl, perhaps the acrylic or methacrylic esters of gallic acid.
In addition, use simultaneously the occasion of polyester polymer, polyvinyl and other binding resins, the resin that has acid number 0.1～50mgKOH/g in preferred all binding resins is more than 60 quality %.
In the present invention, the acid number of the binding resin composition of method for producing toner and toner adopts following method to try to achieve, and basic operation is carried out according to JIS K-0070.
(1) sample uses after removing in advance binding resin (component of polymer) additive in addition, perhaps obtains in advance acid number and the content of the composition beyond binding resin and crosslinked binding resin.Pulverized product 0.5～the 2.0g of accurate weighing sample is take the weight of component of polymer as Wg.For example, when measuring the acid number of binding resin by toner, after measuring in addition the acid number and content of colorant or magnetic etc., try to achieve the acid number of binding resin by calculating.
(2) sample is joined 300(ml) beaker in, add the mixed liquor 150(ml of toluene/ethanol (volume ratio 4/1)), dissolving.
(3) use the ethanolic solution of the KOH of 0.1mol/L, use the potential difference (PD) titration apparatus to carry out titration.
(4) take KOH solution usage at this moment as S(ml), measure simultaneously blank, take KOH solution usage at this moment as B(ml), press following formula (1) and calculate.Wherein, f is the coefficient of KOH concentration.
Acid number (mgKOH/g)=[(S-B) * f * 5.61]/W (1)
The binding resin of toner and the composition that contains binding resin, from the conservatory viewpoint of toner, preferred 35～80 ℃ of glass transition temperature (Tg), particularly preferably 40～75 ℃.If Tg is in this scope, under hot environment, toner is difficult to deteriorated, and is difficult to occur offset printing when adhering to, and tack is good simultaneously.
As operable magnetic in the present invention, the iron oxide that can use the magnetic iron oxide such as (1) magnetic iron ore, maghemite, ferrite and contain other metal oxides.The perhaps metals such as (2) iron, cobalt, nickel, the perhaps alloy of the metals such as these metals and aluminium, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium.(3) and their potpourri etc.
If enumerate the instantiation of magnetic, can exemplify Fe 3O 4, γ-Fe 2O 3, ZnFe 2O 4, Y 3Fe 5O 12, CdFe 2O 4, Gd 3Fe 5O 12, CuFe 2O 4, PbFe 12O, NiFe 2O 4, NdFe 2O, BaFe 12O 19, MgFe 2O 4, MnFe 2O 4, LaFeO 3, iron powder, cobalt powder, nickel powder etc., above-mentioned magnetic can be used in combination separately or more than 2 kinds.Particularly preferred magnetic is the micropowder of tri-iron tetroxide or γ-di-iron trioxide.
In addition, also can use magnetic iron oxide or its potpourris such as the magnetic iron ore that contains the xenogenesis element, maghemite, ferrite.If illustrate the xenogenesis element, can exemplify lithium, beryllium, boron, magnesium, aluminium, silicon, phosphorus, germanium, zirconium, tin, sulphur, calcium, scandium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc, gallium etc.As preferred xenogenesis element, can select from magnesium, aluminium, silicon, phosphorus or zirconium.The xenogenesis element can be included in the lattice of iron oxide, also can be used as oxide and enters into iron oxide, perhaps also can exist as oxide or oxyhydroxide on the surface, preferably contains as oxide.
Above-mentioned xenogenesis element can be regulated pH by when generating magnetic, the salt of various xenogenesis elements being mixed in wherein, makes it to enter in particle.In addition, can perhaps add the salt of various elements and regulate pH by regulating pH after the magnetic particle generates, making it to precipitate into particle surface.
The consumption of above-mentioned magnetic can use magnetic 10～200 mass parts with respect to binding resin 100 mass parts, preferred 20～150 mass parts.The preferred number average particle diameter of these magnetics is 0.1～2 μ m, more preferably 0.1～0.5 μ m.Number average particle diameter can be by using the photo of transmission electron microscope bust shot to try to achieve with mensuration such as digital quantizers.
In addition, as the magnetic characteristic of magnetic, the magnetic characteristic when preferably applying the 10K oersted is respectively coercive force 20～150 oersteds, saturated magnetization 50～200emu/g, residual magnetization 2～20emu/g.
Above-mentioned magnetic also can be used as colorant and uses.As the operable colorant of the present invention, in the situation that black toner can exemplify black or blue dyestuff or pigment particles.As black or blue pigment, carbon black, nigrosine, acetylene black, phthalocyanine blue, indanthrone indigo plant etc. are arranged.As black or blue dyestuff, also can exemplify azo dyes, anthraquinone dyes, oxa anthracenes dyestuff, methylene dye etc.
In the situation of colour with the toner use, colorant can exemplify following substances.As pinkish red colorant, can use condensation azo-compound, diketopyrrolopyrroles compound, anthraquinone compounds, quinacridone compound, basic-dyeable fibre, lake colours, naphthol dye, benzimidazoline ketonic compound, thioindigo compound, perylene compound.particularly, pinkish red colorant as pigment class, can exemplify C.I. paratonere 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 184, 202, 206, 207, 209, C.I. pigment violet 19, C.I. vat red 1, 2, 10, 13, 15, 23, 29, 35, the methyl violet color lake, eosine lake, rhodamine color lake B, alizarine lake, bright carmine lake 3B etc.
Above-mentioned pigment can use separately, but from the image quality aspect of full-colour image, more preferably uses simultaneously dyestuff and pigment to improve its sharpness.
As the pinkish red colorant of dye class, can exemplify the oil-soluble dyess such as C.I. solvent red 1,3,8,23,24,25,27,30,49,81,82,83,84,100,109,121, C.I. disperse red 9, C.I. solvent purple 8,13,14,21,27, C.I. disperse violet 1, C.I. alkali red 1:1,2,9,12,13,14,15,17,18,22,23,24,27,29,32,34,35,36,37,38,39,40, C.I. alkaline purple 1,3,7,10,14,15,21,25,26,27, the basic-dyeable fibres such as 28.
As cyan colorant, can utilize copper phthalocyanine compound and derivant thereof, anthraquinone, basic-dyeable fibre color lake compound.Particularly, the cyan colorant of pigment class is to replace the copper phthalocyanine that 1～5 phthalimidomethyl obtains on C.I. alizarol saphirol 2,3,15,16,17, C.I. reductive blue 6, C.I. acid blue 45 or phthalocyanine frame.Also can use after mixed C .I. pigment Green 7, the greeny colorants such as 12,36,37,38.
As the representative example of phthalocyanine dye, can exemplify C.I. solvent blue 25,55,70, C.I. directly blue 25,86, alkali blue lake, Victoria blue color lake etc.
As yellow colorants, can use condensation azo-compound, isoindoline ketonic compound, anthraquinone compounds, azo metal complex, methylidyne compound, acrylyl amines.Particularly, as yellow pigment, can exemplify C.I. pigment yellow 1,2,3,4,5,6,7,10,11,12,13,14,15,16,17,23,65,73,83,97,180,185, C.I. Vat Yellow 1,3,20, C.I. solvent yellow 16 2, quinoline yellow, tartrazine lake etc.
The consumption of above-mentioned colorant is preferably 0.1～20 mass parts with respect to binding resin 100 mass parts.
After also can mixing with carrier, uses as tow-component developer by toner of the present invention.The carrier that uses in the present invention can use the carriers such as conventional ferrite, magnetic iron ore, also can use resin-coated carrier.
resin-coated carrier is by the resin of support core particle and covering (coating) support core particle surface---and clad material consists of, as the resin that is used for this clad material, optimization styrene-acrylate copolymer, the cinnamic acrylic ester resinoids such as styrene-methacrylate copolymer, acrylate copolymer, the acrylic resins such as methacrylate copolymer, teflon, one chlorotrifluoroethylene polymer, the fluorine resins such as polyvinylidene fluoride, silicones, vibrin, polyamide, the polyvinyl butyrate resin, curable amino acrylate resin, can be also ionomer (iomonomer) resin in addition, polyphenylene sulfides etc. can cover as carrier the resin of (coating) materials'use, these resins can use separately, perhaps also can use multiple.
In addition, also can use the magnetic powder to be dispersed in adhesion type support core in resin.For resin-coated carrier, as the method for using at least resin-coating agent coated carrier wicking surface, can be suitable for resin dissolves or outstanding turbidly apply the method that makes it to be attached on support core, the method for perhaps mixing with the powder state merely after in solvent.The resin-coating material can suitably be determined with respect to the ratio of resin-coated carrier, is preferably 0.01～5 quality % with respect to resin-coated carrier, more preferably 0.1～1 quality %.
As the example with covering (coating) the agent coated magnetic body of potpourri more than 2 kinds, can exemplify (1) and with potpourri 12 mass parts of dimethyldichlorosilane and dimethyl silicon oil (mass ratio 1:5), titanium oxide fine powder 100 mass parts be processed the material that obtains, (2) process to fine silica powder 100 mass parts the material that obtains with potpourri 20 mass parts of dimethyldichlorosilane and dimethyl silicon oil (mass ratio 1:5).
In above-mentioned resin, preferably use potpourri or the silicones of styrene-methylmethacrylate copolymer, fluorine resin and styrene copolymer, particularly preferably silicones.
As the potpourri of fluorine resin and styrene copolymer, (((copolymer quality is than the potpourri of 20～60:5～30:10:50) than 10:90～90:10) and Styrene And Chloroalkyl Acrylates 2-Octyl Nitrite-methylmethacrylate copolymer for copolymer quality than 10:90～90:10) and Styrene And Chloroalkyl Acrylates 2-Octyl Nitrite multipolymer for copolymer quality can to exemplify the potpourri, vinylidene fluoride-TFE copolymer of potpourri, teflon and the styrene-methylmethacrylate copolymer of polyvinylidene fluoride and styrene-methylmethacrylate copolymer.
As silicones, can exemplify the modified silicone resin that the reaction of nitrogenated silicon resin and nitrogenous silane coupling agent and silicones generates.
As the magnetic material of support core, can use the oxides such as ferrite, iron excess type ferrite, magnetic iron ore, gamma-iron oxide, the metals such as iron, cobalt, nickel, or their alloy.In addition, as the element that contains in these magnetic materials, can exemplify iron, cobalt, nickel, aluminium, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten, vanadium.As preferred material, can exemplify copper-zinc take copper, zinc and ferrous components as major component-iron class ferrite, the manganese-magnesium take manganese, magnesium and ferrous components as major component-iron class ferrite.
The resistance value of carrier makes it to reach 10 by the concavo-convex situation of adjusting carrier surface, the amount of resin of coating 6～10 10Ω cm is better.The particle diameter of carrier can use the carrier of 4～200 μ m, preferred 10～150 μ m, more preferably 20～100 μ m.Resin-coated carrier particularly preferably 50% particle diameter is 20～70 μ m.
In tow-component developer, with respect to carrier 100 mass parts, preferably use toner 1～200 mass parts of the present invention, more preferably with respect to carrier 100 mass parts, use toner 2～50 mass parts.
Toner of the present invention also can further contain wax.The wax that uses in the present invention is as described below.For example, the aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low-molecular-weight polypropylene, polyolefin-wax, microcrystalline wax, paraffin, husky rope wax (Sasol Wax).The oxide of the aliphatic hydrocarbon waxes such as oxidized polyethlene wax.Perhaps their segmented copolymer.The vegetable waxs such as candelila wax, palm wax, haze tallow, Jojoba haze tallow.The animal waxs such as beeswax, sheep oil, spermaceti.The mineral waxs such as ceresine, ceresin, vaseline, the wax classes take fatty acid ester as major component such as montanic acid ester type waxes, castor wax.Deoxidation palm wax etc. are with the wax that obtains after part or all of fatty acid ester deoxidation.
As the example of wax, can also exemplify palmitic acid, stearic acid, montanic acid or also have the saturated straight chain fatty acid such as straight-chain alkyl carboxylic acid's class of straight chained alkyl.The unsaturated fatty acids such as brassidic acid, eleostearic acid, parinaric acid.The saturated alcohols such as stearyl alcohol, eicosanol, docosyl alcohol, tetracosanol, ceryl alcohol, mesilyl alcohol or long-chain alkyl alcohol.The polyvalent alcohols such as sorbierite.The fatty acid amides such as linoleic acid acid amides, olefinic acid acid amides, lauric amide.The saturated fatty acid diamides such as methylene two capric acid acid amides, ethylene lauric amide, hexa-methylene distearyl acid acid amides.Ethylene oleamide, hexa-methylene two oleamides, N, N '-two oil base hexane diacid acid amides, N, the unsaturated fatty acid amide-types such as N '-two oil base decanedioic acid acid amides.M-xylene distearyl acid acid amides, N, N '-fragrant same clan diamides such as distearyl m-phthalic acid acid amides.The fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, dolomol.The wax that uses the vinyl monomers such as styrene or acrylate that aliphatic hydrocarbon wax grafting is obtained.The partial esterification compound of the fatty acid such as behenic acid monoglyceride and polyvalent alcohol.By the methyl compound with hydroxyl that the vegetative grease hydrogenation is obtained.
As the wax of preferred use, can exemplify the polyolefin that alkene free radical polymerization is obtained.The polyolefin that obtains after the low molecular weight by-products that obtains during with the high molecular polyolefine polymerization is refining.The polyolefin that under low pressure uses the polymerization catalysts such as Zeigler catalyst (Ziegler ' s catalyst), metalloscene catalyst to obtain.The polyolefin that utilizes radioactive ray, electromagnetic wave or photopolymerization to obtain.The low-molecular-weight polyolefin that the high molecular polyolefine thermal decomposition is obtained.Paraffin, microcrystalline wax, f-t synthetic wax.Adopt the synthetic synthetic chloroflo such as synthol (Synthol) method, iron catalyst fluidized bed synthetic method, Arge method.With the compound of 1 of carbon number as the synthetic wax of monomer, have the hydrocarbon wax of the functional groups such as hydroxyl or carboxyl.Hydrocarbon wax and the potpourri with hydrocarbon wax of functional group.Carry out with vinyl monomers such as styrene, maleate, acrylate, methacrylate, maleic anhydrides the wax that graft modification obtains as parent with these waxes.
In addition, the preferred use these waxes with the wax that pressurization diaphoresis (Press sweating process), solvent method, recrystallization method, vacuum distillation method, supercritical gas extraction method or solution crystallization adjustment (sharpe) molecular weight distribution obtain perhaps removed the wax after low-molecular-weight solid fatty acid, low-molecular-weight solid alcohol, low-molecular-weight solid chemical compound, other impurity.
The wax that uses in the present invention is in order to obtain the balance of tack and anti-offset printing, and preferred fusing point is 70～140 ℃, more preferably 70～120 ℃.If use the wax of this scope fusing point, there is anti-obstruction (blocking) property good, be easy to show the advantage of anti-offset printing effect.
In addition, by uniting different types of wax more than 2 kinds, the effect that can show simultaneously wax---plasticization and the demoulding effect used.
Kind as the wax with plasticization, low-melting wax for example, the wax that perhaps has the wax of branch or have the structure of polar group on molecular structure, as the wax with demoulding effect, can exemplify the high wax of fusing point, on molecular structure for the wax of linear chain structure or do not have the non-polar wax of functional group.As example, can exemplify the fusing point of different waxes more than 2 kinds poor is the combination of the wax of 10 ℃～100 ℃, perhaps combination of polyolefin and graft-modified polyolefin etc.
Select in the situation of 2 kinds of waxes, during the wax of same structure, the wax performance plasticization that relatively molten point is low, the wax performance demoulding effect that fusing point is high.At this moment, the difference of fusing point is in the situation of 10～100 ℃, can effectively show the difference on function.In this case, the fusing point of at least a wax is preferably 70～120 ℃, more preferably 70～100 ℃, the trend that is easy to bring into play the function separating effect is arranged.
In addition, in the molecular structure of wax, relatively the wax of apparatus derivatorius, have the wax of polar group or use the wax performance plasticization of the composition modification different from major component, and the wax of linear chain structure, the non-polar wax that does not have functional group or unmodified pure (straight) wax performance demoulding effect relatively.As preferred combination, can exemplify Natene take ethene as major component or multipolymer and the alkene beyond the ethene as the polyolefin homopolymer of major component or the combination of multipolymer; The combination of polyolefin and graft-modified polyolefin; The combination of alcohol wax, fatty acid wax or ester type waxes and hydrocarbon wax; The combination of f-t synthetic wax or polyolefin-wax and paraffin or microcrystalline wax; The combination of f-t synthetic wax and polyolefin-wax; The combination of paraffin and microcrystalline wax; The combination of palm wax, candelila wax, rice bran wax or montan wax and hydrocarbon wax.
In either case, have the summit temperature of maximum peak in the zone of 70～110 ℃ in the endothermic peak that all preferably observes when the DSC of toner measures, more preferably have maximum peak in the zone of 70～110 ℃.Like this, can easily obtain the balance of toner keeping quality and tack.
In toner of the present invention, the total content of these waxes preferably uses 0.2～20 mass parts with respect to binding resin 100 mass parts, more preferably uses 0.5～10 mass parts, and is more effective like this.
In the present invention, the fusing point of wax is with the summit temperature of the maximum peak of the endothermic peak of the wax measured in the DSC fusing point as wax.
In the present invention, in the DSC of wax or toner measures, preferably measure with high-precision internal heat type power back-off type differential scanning calorimetry.Assay method carries out according to ASTM D3418-82.The DSC curve that uses in the present invention makes it to heat up to lower the temperature and obtains front record, the DSC curve of measuring when then heating up with 10 ℃/min of temperature speed for 1 time.
Also can add fluidity improving agent in toner of the present invention.Fluidity improving agent is by adding the surface of toner to, improving the material of the mobility (become and be easy to flow) of toner.Can exemplify, the fluorine-type resin powder such as carbon black, vinylidene fluoride micro mist, ptfe micropowder, the fine particle silicas such as wet type method for making silicon dioxide, dry type method for making silicon dioxide, the micro mist titanium dioxide, the micro mist aluminium oxide is with processing silicon dioxide, processing titanium dioxide, the processing aluminium oxide after its use silane coupling agent, titanium coupling agent or silicone oil enforcement surface treatment.Wherein, preferred fine particle silica, micro mist titanium dioxide, micro mist aluminium oxide in addition, are more preferably implemented processing silicon dioxide after surface treatment with silane coupling agent or silicone oil to it.The particle diameter of fluidity improving agent is as preferred 0.001～2 μ m of average primary particle diameter, particularly preferably 0.002～0.2 μ m.
Preferred fine particle silica is the powder body that silicon halogen compounds generates by gaseous oxidation, namely is called as the material of dry process silicon dioxide or pyrogenic silica.
The commercially available fine silica powder that generates by gaseous oxidation as silicon halogen compounds is for example with the commercially available product of following trade name.AEROSIL(Japan Aerosil Co., Ltd. system, below identical)-130 ,-300 ,-380 ,-TT600 ,-MOX170 ,-MOX80 ,-COK84, Ca-O-SiL(CABOT Co., Ltd. system, below identical)-M-5 ,-MS-7 ,-MS-75 ,-HS-5 ,-EH-5, Wacker HDK(WACKER-CHEMIEGMBH Co., Ltd. system, below identical)-N20 V15 ,-N20E ,-T30 ,-T40, D-CFineSilica(Dow Corning Toray Co., Ltd. system); Fransol(Fransil Co., Ltd. system).
And the fine silica powder that more preferably silicon halogen compounds is generated by gaseous oxidation carries out the processing fine silica powder after hydrophobization is processed.In processing fine silica powder, particularly preferably fine silica powder is processed, so that the hydrophobization degree of measuring by the methyl alcohol burette test shows the material that 30～80% value obtains ideally.Hydrophobization carries out chemistry with the organo-silicon compound of fine silica powder reaction or physisorption etc. or physical treatment is implemented by using.As preferred method, it can be the method that the fine silica powder that silicon halogen compounds generates by gaseous oxidation is processed with organo-silicon compound.
as organo-silicon compound, the hydroxypropyl trimethoxy silane is arranged, phenyltrimethoxysila,e, the n-hexadecyl trimethoxy silane, n-octadecane base trimethoxy silane, the vinyl methoxy silane, vinyltriethoxysilane, vinyltriacetoxy silane, the dimethyl vinyl chlorosilane, the divinyl chlorosilane, γ-metacryloxy propyl trimethoxy silicane, hexamethyldisilane, trimethyl silane, trimethyl chlorosilane, dimethyldichlorosilane, methyl trichlorosilane, allyldimethylcholrosilane, the allyl phenyl dichlorosilane, the benzyl dimethyl chlorosilane, the bromomethyl dimethylchlorosilane, α-chloroethyl trichlorosilane, β-chloroethyl trichlorosilane, CMDMCS chloromethyl dimethyl chlorosilane, three Organosilyl mercaptan, trimethyl silyl mercaptan, three Organosilyl acrylate, vinyl-dimethyl base acetoxylsilane, dimethylethoxysilane, trimethylethoxysilane, the trimethyl methoxy silane, methyl triethoxysilane, the isobutyl trimethoxy silane, dimethyldimethoxysil,ne, the diphenyl diethoxy silane, HMDO, 1,3-divinyl tetramethyl disiloxane, 1,3-diphenyl tetramethyl disiloxane, and 1 molecule has 2 to 12 siloxane units, and the unit that is positioned at end contains respectively the dimethyl polysiloxane etc. of the hydroxyl of the upper combination of 0～1 Si.And, can also exemplify dimethyl-silicon wet goods silicone oil.These organo-silicon compound can use a kind, perhaps use as the potpourri more than 2 kinds.
The preferred number average particle diameter of fluidity improving agent reaches 5～100nm, more preferably 5～50nm.Adopt the specific surface area of the nitrogen absorption of BET method mensuration to be preferably 30m 2More than/g, more preferably 60～400m 2/ g, as the micro mist after surface treatment, preferred 20m 2More than/g, 40～300m particularly preferably 2/ g.The preferred dosage of these micro mists is preferably 0.03～8 mass parts with respect to toner particle 100 mass parts.
In toner of the present invention; as other adjuvants; in order to protect photoreceptor and carrier, raising spatter property, adjusting thermal characteristics, electrical characteristics and physical characteristics, regulating resistance, adjusting softening point, to improve adhesive rate etc.; can add as required various metallic soaps, fluorine class surfactant, dioctyl phthalate; as the electric conductivity imparting agent; can add as required tin oxide, zinc paste, carbon black, antimony oxide etc., or the inorganic micro powder such as titanium dioxide, aluminium oxide, aluminium oxide etc.In addition, these inorganic micro powders also can carry out hydrophobization as required.In addition, also can use on a small quantity the lubricants such as teflon, zinc stearate, polyvinylidene fluoride, lapping compound, the anticaking agent such as cesium oxide, silit, strontium titanates, and be the white particles of opposite polarity and black particle as the developability improving agent with toner particle.
In order to control the purposes such as carried charge, these adjuvants are also preferably processed with the treating agents such as silicone varnish, various modified polyorganosiloxane varnish, silicone oil, various modified silicon oil, silane coupling agent, the silane coupling agent with functional group, other organo-silicon compound or various treating agent.
Charge control agent of the present invention and above-mentioned adjuvant and toner one are reinstated the abundant mix and blends of mixer such as Henschel mixer (Henschel mixer), bowl mill, nauta mixer (Nauta mixer), V-Mixer, Wtypeofblender, super mixer, toner particle surface uniform ground is carried out adding processing outward, also can obtain required development of static charge toner.
Toner of the present invention is to thermally-stabilised, and the variation that electronic photo can not be heated when processing can keep stable charged characteristic.In addition, but due to equal Uniform Dispersion in any binding resin, thereby new the charged of toner distributes very evenly.Therefore, though toner of the present invention in the situation that to be transferred, reclaim toner (used toner), compare with new toner, saturated friction belt electric weight, charged distribution also can change hardly.Recycling is by development of static charge of the present invention during with out used toner of toner, contain the vibrin of aliphatic diol as binding resin by selection, perhaps with the copolymer in cinnamic acrylic ester of metal corsslinking as binding resin, adopt to add wherein a large amount of polyolefinic methods to make toner, can further dwindle the gap between new toner and used toner.
Method as making toner of the present invention can adopt known autofrettage to make.If manufacture method is given an example, preferably the above-mentioned toner constituent materials such as binding resin, charge control agent, colorant are fully mixed with mixers such as bowl mill, this potpourri is fully mixing with heating kneading devices such as hot-rolling kneaders, cooling curing, after pulverizing, the method (comminuting method) that classification obtains.
In addition, also can adopt said mixture to be dissolved in solvent make it micronize by spraying, drying, the method that classification obtains is made.And, by mix the material of regulation in the monomer that consists of binding resin, emulsification or make suspension after, make it the toner autofrettage of utilizing polymerization that polymerization obtains toner, in the so-called micro-capsule toner that is consisted of by core material and shell material, make core material or shell material or the two contain the method for prescribed material, also can make.And, by as required required adjuvant fully being mixed with mixers such as Henschel mixers with toner particle, also can make toner of the present invention.
If illustrate in greater detail the autofrettage of the toner of the present invention that utilizes above-mentioned comminuting method, at first binding resin is evenly mixed with colorant, charge control agent, other necessary adjuvants.Mixing can be adopted known stirring machine, and such as Henschel mixer, super mixer, bowl mill etc. mixed.The potpourri that obtains is carried out heat fusing with the extruder of the kneader of closed or single shaft or twin shaft mixing.After mixing thing is cooling, carry out coarse crushing with mulling machine or hammer-mill, then carry out Crushing of Ultrafine with comminutors such as jet mill, high speed rotating vanes mullers.Then; use air classifier; such as the particulate classifier (microplex) of the elbow nozzle (elbow jet) of the inertial classification mode of utilizing wall attachment effect (Coanda effect), cyclone (centrifugal) hierarchical approaches, DS grader etc., carry out classification until reach the granularity of regulation.In addition, when with additive etc., toner surface being processed, use homo-mixer, such as Henschel mixer, super mixer etc., toner and additive are mixed.
In addition, toner of the present invention also can adopt outstanding turbid polymerization or emulsion polymerization method manufacturing.In outstanding turbid polymerization, with polymerizable monomer, colorant, polymerization initiator, charge control agent and crosslinking chemical as required, other adjuvant uniform dissolution or dispersions, after being mixed with monomer composition, use suitable stirring machine or dispersion machine, such as homo-mixer (homomixer), refiner, atomizer, microjet homogenizer (microfluidizer), single liquid fluid tip, gas-liquid fluid tip, electronic mulser etc., make it to be dispersed in the external phase that contains this monomer composition and dispersion stabilizer, for example aqueous phase.Preferred adjusting stirring rate, temperature, time make the drop of polymerizable monomer composition have the size of required toner particle, carry out granulation.Simultaneously carry out polyreaction under 40～90 ℃, can obtain having the toner particle of required particle diameter.After the toner particle that obtains is washed, filters, carry out drying.Making outer after toner particle adds processing and can adopt the method for putting down in writing previously.
If utilize emulsion polymerization method manufacturing, owing to comparing with the particle that utilizes above-mentioned outstanding turbid polymerization to obtain, although excellent in uniform, but mean grain size is very little, be 0.1～1.0 μ m, therefore also can be according to circumstances, by take emulsified particle as core, rear interpolation polymerizable monomer makes the so-called core polymerization of grain growth, perhaps makes the method manufacturing that emulsified particle is coalescent, be fused into suitable mean grain size.
These manufacturings of adopting polymerizations are due to without pulverizing process, thereby there is no need to give fragility to toner particle, and can use in a large number unworkable low softening point material in the past comminuting method, therefore can widen the range of choice of material.Therefore the release agent of hydrophobic material and colorant are difficult to be exposed to surfaces of toner particles, can reduce toner formed article, photoreceptor, transfer roll or decide the pollution of device.
By adopting polymerization to make toner of the present invention, can further improve the characteristics such as image reproducing, transfer printing, color reproduction, for the small point of correspondence, the particle diameter of toner is dwindled, can obtain with comparalive ease the toner of narrow particle size distribution.
The polymerizable monomer that uses when adopting polymerization to make toner of the present invention, can use can free radical polymerization vinyl-based polymerizable monomer.As this vinyl-based polymerizable monomer, can use simple function polymerizable monomer or multi-functional polymerizable monomer.
as the simple function polymerizable monomer, can exemplify styrene, α-methyl styrene, Beta-methyl styrene, o-methyl styrene, a methyl styrene, p-methylstyrene, 2,4-DMS, align butylstyrene, p-tert-butylstyrene, to positive hexyl phenenyl ethene, to phenylethylene polymerization monomers such as styryl phenyls, methyl acrylate, ethyl acrylate, the acrylic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, the acrylic acid n-pentyl ester, the just own ester of acrylic acid, 2-EHA, the acrylic acid n-octyl, the acrylic acid benzene methyl, dimethyl phosphate methyl acrylate (dimethylphosphate methyl acrylate), dibutylphosphoric acid ester ethyl acrylate (dibutylphosphate ethyl acrylate), the propylene vinegar Type of Collective monomers such as acrylic acid 2-benzoyloxy ethyl ester, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n propyl methacrylate, isopropyl methacrylate, n-BMA, isobutyl methacrylate, Tert-butyl Methacrylate, the methacrylic acid n-pentyl ester, the just own ester of methacrylic acid, 2-Ethylhexyl Methacrylate, n octyl methacrylate, methacrylic acid di(2-ethylhexyl)phosphate ethyl ester (diethylphosphate methacrylate), the metering system vinegar Type of Collective monomers such as dibutylphosphoric acid ester β-dimethyl-aminoethylmethacrylate (dibutylphosphate ethyl methacrylate), unsaturated aliphatic monocarboxylic esters class, the vinyl esters such as vinyl acetate, propionate, vinyl benzoate, the vinyl ethers such as vinyl methyl ether, vinyl isobutyl ether, the vinyl ketones such as ethenyl methyl ketone, vinyl hexyl ketone, vinyl nezukone.
The water soluble starter that uses when making toner of the present invention as the employing polymerization, can exemplify ammonium persulfate, potassium persulfate, 2,2 '-azo, two (N, N '-dimethylene NSC 18620) hydrochloride, 2,2 '-azo two (amino two propane of 2-) hydrochloride, azo two (isobutyl amidine) hydrochloride, 2,2 '-azoisobutyronitrile sodium sulfonate, ferrous sulphate or hydrogen peroxide.
Polymerization initiator preferably adds 0.5～20 mass parts with respect to polymerizable monomer 100 mass parts, can separately or unite use.The spreading agent that uses during as the manufacturing polymerization toner, for example, as the mineral-type oxide, can exemplify tricalcium phosphate, magnesium phosphate, aluminum phosphate, trbasic zinc phosphate, calcium carbonate, magnesium carbonate, aluminium hydroxide, calcium metasilicate, calcium sulphate, barium sulphate, bentonitic clay, silicon dioxide, aluminium oxide etc.As the organic compound, can use sodium salt, starch of polyvinyl alcohol (PVA), gelatin, methylcellulose, methylhydroxypropylcellulose, ethyl cellulose, carboxymethyl cellulose etc.These spreading agents preferably use 0.2～2.0 mass parts with respect to polymerizable monomer 100 mass parts.
These spreading agents also can directly use commercially available material, in order to obtain having the dispersed particle of tiny uniform granularity, also can generate this mineral compound in dispersion medium under high-speed stirred.
The toner that obtains according to above-mentioned polymerization does not carry out the toner that the special comminuting method of processing obtains and compares with adopting, the little trend of concavo-convex degree that toner particle is arranged, owing to being amorphous, thereby increase by the contact area that electrostatic latent image supports body and toner, thereby the adhesion of toner increases, machine internal contamination as a result reduces, and easily obtains the image that image color is higher, quality is higher.
In addition, for the toner that adopts comminuting method to obtain, also can exemplify by toner particle being scattered in the hot bath method that heats in water, making it by the heat treating process in thermal current or giving the method that physical shock method that mechanical energy processes etc. reduces the concavo-convex degree of toner surface.---the HYBRIDIZER(nara machinery is made Co., Ltd. of institute system), have the mixer of high-speed stirred blade---Henschel mixer etc. as effectively installing, can exemplify the micro mist emerging system (Mechanofusion System) that utilizes the dry-type mechanical chemical method (Hosokawa Micron Co., Ltd. system), I formula jet mill to reducing concavo-convex degree, having the mixing arrangement of roller and liner.
As one of the value of the concavo-convex degree of the above-mentioned toner particle of expression, can show with average circular kilsyth basalt.Average circularity (C) refers to, obtains circularity (Ci) by following formula (2), the value that obtains divided by all particles number (m) of mensuration with the circularity summation of all particles of mensuration shown in following formula (3) for another example.
[several 1]
Figure 716468DEST_PATH_IMAGE002
[several 2]
Figure 181691DEST_PATH_IMAGE003
Above-mentioned circularity (Ci) uses air-flowing type particle image analytical equipment (for example, the FPIA-1000 processed of East Asia Medical Electronics Co., Ltd) to measure.As assay method, approximately disperse approximately 5mg of toner in the water 10ml of 0.1mg being dissolved with non-ionics, the configuration dispersion liquid, to dispersion liquid irradiation ultrasound wave (20kHz, 50W) 5 minutes, make dispersion liquid concentration reach 5000～20000/μ L, use said flow formula particle image determinator, measure that to have 0.60 a μ m above and distribute lower than the circularity of the particle of the projected area equivalent diameter of 159.21 μ m.
The value of above-mentioned average circularity is preferably 0.955 to 0.990, more preferably toner particle is adjusted to 0.960 to 0.985, will reduce like this phenomenon that the transfer printing residual toner increases, and is difficult for causing transfer printing again.
The occasion of toner of the present invention, productivity aspect from image and toner, using when measuring such as laser type particle size distribution machines such as micron sifters (Micron Sizer) (such as Co., Ltd. of Seishin enterprise system), the mean grain size of the particle diameter preferred volume standard of toner is 2～15 μ m.3～12 μ m more preferably.If use the toner of the mean grain size of this scope, resolution and sharpness are good, and the yield rate when making toner is good, and the problem such as in can generator, toner disperses, skin soaks into, thereby preferred.
Size-grade distribution about toner, the occasion of toner of the present invention, for example utilize Coulter-counter (the Coulter TA-II processed of Co., Ltd.) when carrying out granulometry, the following particle content of 2 μ m preferably by the number standard be the above particle content of 10～90%, 12.7 μ m preferably by volume standard be 0～30%.
Development of static charge of the present invention is with the occasion of toner, and the specific surface area of toner is preferably 1.2～5.0m in the attached gas of desorption is the BET specific area measuring of nitrogen 2/ g.1.5～3.0m more preferably 2/ g.The mensuration of specific surface area for example uses BET specific area measuring device (for example, Shimadzu Scisakusho Ltd's system, FlowSorbII2300), be defined as and breaking away from the adsorbed gas of toner surface under 50 ℃ after 30 minutes, with liquid nitrogen quenching absorption nitrogen again, and then be warming up to 50 ℃, the value of being tried to achieve by amount of gas evolved at this moment.
The occasion of toner of the present invention uses powder property tester (Powder tester) (Hosokawa Micron Co., Ltd. system) to measure apparent specific gravity (volume density).The occasion of nonmagnetic toner, preferred 0.2～0.6g/cm 3, the occasion of magnetic color tuner, different according to kind and the content of magnetic powder, preferred 0.2～2.0g/cm 3
The occasion of toner of the present invention, in the situation that nonmagnetic toner, the preferred 0.9～1.2g/cm of absolute specific gravity 3, in the situation that magnetic color tuner is different according to kind and the content of magnetic powder, it is desirable to 0.9～4.0g/cm 3The following calculating of the absolute specific gravity of toner.Accurate weighing toner 1.000g puts it in the tablet former of 10mm Φ, applies 200kgf/cm under vacuum condition 2Compression forming in the time of pressure.Measure the height of this cylindric article shaped with micrometer, calculate thus absolute specific gravity.
Mobile angle of repose and the definition of static angle of repose that the mobility of toner is measured by for example angle of repose determinator (for example cylinder well physics and chemistry Co., Ltd. system).The development of static charge of use charge control agent of the present invention is spent with the occasion of toner, preferred 5 degree～45 in the angle of repose of flowing.In addition, preferred 10～50 degree in static angle of repose.
Toner of the present invention is the occasion of crush type toner, and the mean value of shape coefficient (SF-1) is preferably 100～400, shape coefficient 2(SF-2) mean value be preferably 100～350.
In the present invention, SF-1, the SF-2 of the shape coefficient of expression toner refer to, use the optical microscope (for example BH-2 processed of Olympus Co., Ltd) that for example possesses the CCD camera to take a sample, make the toner particle group who is amplified to 1000 times in a visual field reach the degree of 30, with the image transmitting that obtains to image analysis apparatus (for example Nireco Luzex FS processed of Co., Ltd.), toner particle is repeated identical operation until reach approximately 1000, calculate shape coefficient.Shape coefficient (SF-1) and shape coefficient 2(SF-2) be calculated as follows.
SF-1=（（ML 2×π）/4A）×100
(in formula, ML represents greatly enhancing most of particle, and A represents the projected area of a particle.）
SF-2=（PM 2/4Aπ）×100
(in formula, PM represents the girth of particle, and A represents the projected area of a particle.）
SF-1 represents the distortion of particle, and particle is got over subglobular, and numerical value is more near 100, and elongated, numerical value is larger.In addition, SF-2 represents the concavo-convex of particle, and particle is got over subglobular, and numerical value is more near 100, and the shape of particle is more complicated, and numerical value is larger.
The specific insulation of toner of the present invention, in the situation that nonmagnetic toner, preferred 1 * 10 12～1 * 10 16Ω cm, in addition, in the situation that magnetic color tuner is different according to kind and the content of magnetic powder, preferred 1 * 10 8～1 * 10 16Ω cm.The specific insulation of toner at this moment is defined as, with the toner particle compression forming, make the discoid test specimen of diameter 50mm, thick 2mm, it is arranged on solid with on electrode (for example SE-70 processed of Ando Electric Co., Ltd), use high insulating-resistance meter (for example Hewlett-Packard 4339A processed of Co., Ltd.), when applying continuously DC voltage 100V through the value after 1 hour.
The dielectric loss tangent of toner of the present invention (dielectric tangent), in the situation that nonmagnetic toner, preferred 1.0 * 10 -3～15.0 * 10 -3, in addition, in the situation that magnetic color tuner is different according to kind and the content of magnetic powder, preferred 2 * 10 -3～30 * 10 -3At this moment toner specific insulation is defined as, with the toner particle compression forming, make the discoid test specimen of diameter 50mm, thick 2mm, it is arranged on solid with on electrode, use LCR measuring appliance (for example Hewlett-Packard 4284A processed of Co., Ltd.), the dielectric loss tangent value (Tan δ) that obtains when measuring under measuring frequency 1KHz, peak-to-peak voltage 0.1KV.
Ai Zuoshi (Izod) impact value of the preferred toner of toner of the present invention is 0.1～30kgcm/cm.The Ai Zuoshi impact value of toner at this moment refers to, with the toner particle hot melt, is made into tabular test specimen, according to the impulse test method of JIS specification K-7110(rigid plastic) it is measured.
The melt index of the preferred toner of toner of the present invention (MI value) is 10～150g/10min.The melt index of toner at this moment (MI value) refers to the method according to JIS specification K-7210(A) value measured.At this moment, measuring temperature is 125 ℃, and load-carrying is 10kg.
It is 80～180 ℃ that the melting of the preferred toner of toner of the present invention begins temperature, and 4mm reduces preferred 90～220 ℃ of temperature.The melting of toner at this moment begins temperature and is defined as, with the toner particle compression forming, be made into the cylindric test specimen of diameter 10mm, thick 20mm, it is arranged on the heat fusing characteristic detecting apparatus, melting point analyzer (for example CFT-500C processed of Shimadzu Scisakusho Ltd) for example is at load-carrying 20kgf/cm 2Under begin the value that melting, piston begin to reduce when measuring.In addition, adopt same mensuration, the temperature when piston is reduced 4mm is defined as 4mm and reduces temperature.
The glass transition temperature (Tg) of the preferred toner of toner of the present invention is 35～80 ℃, more preferably 40～75 ℃.The glass transition temperature of toner at this moment is defined as, and uses differential thermal analysis (being designated hereinafter simply as DSC) device to measure, by the temperature that heats up under uniform temperature afterwards, the peak value of quenching, the phase change that shows when heating up is again obtained.If the Tg of toner is in above-mentioned scope, anti-offset printing and storage stability are good, and fixing strength is also good, thereby preferred.
In the DSC of toner of the present invention measured, in the endothermic peak that preferably observes, there was the summit temperature of maximum peak in the zone of 70～120 ℃.
The melt viscosity of the preferred toner of toner of the present invention is 1000～50000 pools, more preferably 1500～38000 pools.The melt viscosity of toner at this moment is defined as, with the toner particle compression forming, be made into the cylindric test specimen of diameter 10mm, thick 20mm, it is arranged on the heat fusing characteristic detecting apparatus, melting point analyzer (for example CFT-500C processed of Shimadzu Scisakusho Ltd) for example is at load-carrying 20kgf/cm 2Under value when measuring.
Insoluble composition 0～30 quality % of the preferred THF of dissolution with solvents residue of toner of the present invention, insoluble composition 0～40 quality % of ethyl acetate, insoluble composition 0～30 quality % of chloroform.Dissolution with solvents residue wherein is for toner 1g uniform dissolution/or be dispersed in the various solvent 100ml of THF, ethyl acetate and chloroform, to this solution/or dispersion liquid carry out press filtration, dried filtrate, quantitatively, calculate by this value the value that the ratio of the material that is insoluble to organic solvent in toner obtains.
Toner of the present invention can be used for a kind of of image forming method---single composition visualization way.Single composition visualization way refers to the toner supply sub-image of filming is supported the mode that body makes image development.The filming of toner is usually used to be possessed toner transfer unit, toner bed thickness control assembly and toner and replenishes accessory, and should replenish the device that is connected respectively between accessory and toner transfer unit and toner bed thickness control assembly and toner transfer unit and carry out.
Below illustrate the situation that toner of the present invention is applicable to two composition development methods.Two composition visualization way refer to use the mode of toner and carrier (having the material of giving the effect of material and toner conveying material as charged), and carrier can use above-mentioned magnetic material or beaded glass.Developer (toner and carrier) produces the quantity of electric charge of regulation by stirring with mixing component, utilizes magnetic roller etc. to be delivered to the development position.On left magnetic roller, developer remains on the roller surface by magnetic force, controls to the magnetic brush of suitable height by the formation such as developer control panel layer.Developer moves on roller along with the rotation of developer roll, contacts with static charge sub-image holder, perhaps stands facing each other mutually with contactless state with certain interval, makes image development visual.In situation with the contactless state development, usually produce DC electric field by making between developer and sub-image holder, toner can obtain the driving force of circling in the air in the space of certain intervals, but obtains image more clearly in order to develop, and also can be suitable for the mode that stack exchanges.
In addition, charge control agent of the present invention also is suitable for use as the charge control agent (charge enhancers) in static powder body coating use coating.That is to say, the electrostatic coating that uses this charge enhancers is environment resistant with coating, storage stability, particularly thermal stability and permanance good, transfer efficiency of coatings reaches 100%, can form the thick film that there is no paint film defect.
Embodiment 1
Below in conjunction with embodiment, the present invention is described, but these embodiment to the present invention without any restriction.In an embodiment, " part " all represents " mass parts ".
possessing stirring machine, cooling tube, add 4-TBP 120.2g(0.8 mole in the 1L four neck flasks of thermometer and gas introduction tube), free sulfur 51.3g(1.6 mole) and NaOH 16.0g(0.4 mole), add wherein diphenyl ether 360.5g, when stirring in nitrogen stream, remain in 130 ℃, water and sulfuretted hydrogen that the limit generates except dereaction, reacted 1 hour on the limit, then be warming up to 170 ℃, water and sulfuretted hydrogen that the limit generates except dereaction, limit reaction 1 hour, be warming up to again 230 ℃, water and sulfuretted hydrogen that the limit generates except dereaction, limit reaction 18 hours.This reaction mixture is cooled to room temperature, and after adding the aqueous sulfuric acid 80ml of 3 moles/L to be hydrolyzed, (88/12, mixed solvent 200ml v/v) makes it to separate out coarse crystal to add isopropanol/water.Filter to take out coarse crystal, with the coarse crystal that obtains with isopropanol/water (88/12, mixed solvent 200ml washing v/v) 1 time, water 240ml washing 2 times, then use isopropanol/water (88/12, mixed solvent 200ml washing v/v) 1 time.Spend the night at 120 ℃ of lower drying under reduced pressure, obtain crude product 113.2g.
The ratio of components of the crude product that obtains by high performance liquid chromatography (being designated hereinafter simply as HPLC) determination and analysis.The condition determination of HPLC is as described below.Device: the LC-6A processed of Shimadzu Scisakusho Ltd, post: the Develosil ODS-HG-5(processed of wild village KCC internal diameter 4.6, column length 250mm), column temperature: 40 ℃, mobile phase: THF/ acetonitrile/water/trifluoroacetic acid=450/400/150/2(v/v/v/v), flow velocity: 1.0ml/ divides, injection rate IR: 1 μL, sample concentration: 1000ppm.
By the analysis result of HPLC as can be known, above-mentioned crude product is that 4 times of bodies of ring-type that R is that the tert-butyl group, m are 4 in general formula (1), n is 0, Y be all hydrogen atom show peak area ratios 96.1%, and in general formula (1), R is that the tert-butyl group, m are 8, n is 0, Y is all the potpourri of 8 times of bodies demonstration peak area ratios 3.6% of ring-type of hydrogen atom.
Crude product 100g is scattered in THF200ml, at room temperature stirs and spend the night.After filtering the collection crystal, wash with THF90ml.Crystal is spent the night at 120 ℃ of lower drying under reduced pressure, obtain highly finished product 83.6g.Adopt above-mentioned HPLC condition determination to analyze highly finished product, the peak area ratio that in general formula (1), R is that the tert-butyl group, m are 4 as a result, n is 0, Y is all 4 times of bodies of ring-type of hydrogen atom is 99.1%.
Add above-mentioned highly finished product 8.65g(0.012 mole in 500ml four neck flasks), add boric acid 6.18g(0.1 mole) and potassium hydroxide 2.81g(0.05 mole) be dissolved in borate buffer (pH8.5 ~ 8.6) 300ml for preparing in water 1L after, be heated to 50 ℃.With dripping outstanding turbid in above-mentioned borate buffer (pH8.5 ~ 8.6) 100ml zinc chloride 1.64g(0.012 mole in 1 hour).The pH that drips after finishing is 6.Stir after 5 hours when being heated to 50 ℃, be cooled to room temperature.After filtration under diminished pressure collecting reaction product, water 50ml washing 3 times, at 120 ℃ of lower drying under reduced pressure, obtain in the general formula (1) of white powder shape R and be the tert-butyl group, m and be 4, n is 0, Y is the compounds of this invention 9.17g of zinc.
Embodiment 2
Add embodiment 1 to obtain in 500ml four neck flasks above-mentioned highly finished product 8.65g(0.012 mole), after adding above-mentioned borate buffer (pH8.5 ~ 8.6) 300ml, be heated to 50 ℃.With dripping outstanding turbid in above-mentioned borate buffer (pH8.5 ~ 8.6) 100ml cobalt acetate tetrahydrate 2.99g(0.012 mole in 10 minutes).After dripping the cobalt acetate of deep pink, reactant liquor is varied to light blue.The pH that drips after finishing is 7.5.Stir after 4 hours when being heated to 50 ℃, be cooled to room temperature.After filtration under diminished pressure collecting reaction product, water 50ml washing 3 times, at 120 ℃ of lower drying under reduced pressure, obtain with R in the general formula (1) of dark brown yellow powder shaped be that the tert-butyl group, m are 4, n is 0, Y is the compounds of this invention 9.29g of cobalt.
Embodiment 3
In the 500ml four neck flasks with stirring machine, cooling tube, thermometer, add that R in general formula (1) is that the tert-butyl group, m are 4, n is 0, Y be all hydrogen atom cyclic phenol sulfide 56.2g(0.078 mole), acetic acid 224.8g(4 times wt/wt), sodium tungstate 2 hydrate 5.15g(0.0156 mole), sodium acetate 3 hydrate 5.31g(0.039 mole), be warming up to 60 ℃ in stirring.When stirring with approximately 35% aqueous hydrogen peroxide solution 121.2g(1.248 mole of dropping in the flask in 1.5 hours).After dripping end, after stirring 15 hours under 60 ℃, then stirred 15 hours under 70 ℃.Then, dripping 36% hydrochloric acid 15.8g(0.156 mole under 80 ℃ when stirring) after, then stirred 1 hour under 80 ℃.Be cooled to room temperature, separate out white solid.Filtration under diminished pressure is collected white solid, after water 80ml washing 3 times, vacuum drying (80 ℃, 24 hours), obtain in general formula (1) R and be the tert-butyl group, m and be 4, n is 2, Y is all 4 times of body 58.3g(yields 88% of oxidized cyclic of hydrogen atom).
The analysis of the 4 times of bodies of oxidized cyclic that obtain adopts HPLC mensuration to carry out.The condition determination of HPLC is as described below.Device: the LC-6A processed of Shimadzu Scisakusho Ltd, post: the Develosil ODS-HG-5(processed of wild village KCC internal diameter 4.6, column length 250mm), column temperature: 40 ℃, mobile phase: THF/ acetonitrile/water/trifluoroacetic acid=350/350/300/2(v/v/v/v), flow velocity: 1.0ml/ divides, injection rate IR: 1 μL, sample concentration: 1000ppm.
By the analysis result of HPLC as can be known, the peak area ratio that in general formula (1), R is that the tert-butyl group, m are 4, n is 2, Y is all 4 times of bodies of oxidized cyclic of hydrogen atom is 99.3%.
Add 4 times of body 8.49g(0.01 of above-mentioned oxidized cyclic moles in 500ml four neck flasks) and water 370g after, be heated to 50 ℃.Dropping 10%(w/v) the NaOH aqueous solution is 7.98g(0.02 mole).In the milk yellow suspension that obtains with dripping 38%(w/v in 2.5 hours) ferric chloride in aqueous solution 4.28g(0.01 mole).Reactant liquor becomes empurpled suspension (pH=3).Stir after 3 hours when being heated to 50 ℃, be cooled to room temperature.After filtration under diminished pressure collecting reaction product, water 50ml washing 3 times, at 120 ℃ of lower drying under reduced pressure, obtain in the general formula (1) of dark brown powder shaped R and be the tert-butyl group, m and be 4, n is 2, Y is the compounds of this invention 8.97g of iron.
Embodiment 4
Add embodiment 3 to obtain in 500ml four neck flasks 4 times of body 8.49g(0.01 of above-mentioned oxidized cyclic moles), after adding above-mentioned borate buffer (pH8.5～8.6) 300ml, be heated to 50 ℃.Dripped calcium chloride dihydrate 1.47g(0.01 mole that is dissolved in above-mentioned borate buffer (pH8.5～8.6) 100ml with 2 hours).The pH that drips after finishing is 7.5～8.Stir after 1.5 hours when being heated to 50 ℃, be cooled to room temperature.After filtration under diminished pressure collecting reaction product, water 50ml washing 3 times, at 120 ℃ of lower drying under reduced pressure, obtain in the general formula (1) of white powder shape R and be the tert-butyl group, m and be 4, n is 2, Y is the compounds of this invention 9.12g of calcium.
Embodiment 5
1 part of the zinc compound of the cyclic phenol sulfide that 94 parts of cinnamic acrylic ester analog copolymer resins (CPR-100 processed of Mitsui Chemicals, Inc), embodiment 1 is synthetic, the heating and mixing device melting mixing of 110 ℃ of 5 parts of use of carbon black (MA-100 processed of Mitsubishi chemical Co., Ltd) are carried out coarse crushing with cooling potpourri with hammer-mill.After carrying out Crushing of Ultrafine with jet mill again, classification obtains the black toner of mean grain size 10 ± 0.5 μ m of dimension criteria.According to 4 parts of this toners, the ratio mixing of 100 parts, the ferrite carrier (Powdertech F-150 processed of Co., Ltd.) that do not coat, vibration, after making toner electronegative, measure time constant, the saturated zone electric weight that represents electric rising (charging risetime) with Blow-off body of powder electrification amount determining device under the environment of 25 ℃ of temperature, humidity 50%.The results are summarized in table 1.
[Comparative examples A]
In order to compare, the zinc compound of the cyclic phenol sulfide that embodiment 1 is synthetic replaces to 4 times of bodies of above-mentioned ring-type that embodiment 1 obtains (in general formula (1), R is that the tert-butyl group, m are 4, n is 0, Y be all 4 times of bodies of ring-type of hydrogen atom), after making toner according to method similarly to Example 5, minute constant, saturated zone electric weight.The results are summarized in table 1.
[comparative example B]
In order to compare, the zinc compound of the cyclic phenol sulfide that embodiment 1 is synthetic replaces to 4 times of bodies of ring-type (in general formula (1), R is that the tert-butyl group, m are 4, n is 2, Y be all 4 times of bodies of oxidized cyclic of hydrogen atom) of the above-mentioned oxidized form that embodiment 3 obtains, after making toner according to method similarly to Example 5, minute constant, saturated zone electric weight.The results are summarized in table 1.
Embodiment 6
The zinc compound of the cyclic phenol sulfide that embodiment 1 is synthetic replaces to the cobalt compound of the synthetic cyclic phenol sulfide of embodiment 2, after making toner according to method similarly to Example 5, and minute constant, saturated zone electric weight.The results are summarized in table 1.
Embodiment 7
The zinc compound of the cyclic phenol sulfide that embodiment 1 is synthetic replaces to the iron compound of the synthetic oxidized cyclic phenol sulfide of embodiment 3, after making toner according to method similarly to Example 5, and minute constant, saturated zone electric weight.The results are summarized in table 1.
Embodiment 8
The zinc compound of the cyclic phenol sulfide that embodiment 1 is synthetic replaces to the calcium compound of the synthetic oxidized cyclic phenol sulfide of embodiment 4, after making toner according to method similarly to Example 5, and minute constant, saturated zone electric weight.The results are summarized in table 1.
[comparative example 1]
In order to compare, the zinc compound of the cyclic phenol sulfide that embodiment 1 is synthetic replaces to salicylic zinc complex, after making toner according to method similarly to Example 5, and minute constant, saturated zone electric weight.The results are summarized in table 1.
[comparative example 2]
In order to compare, the zinc compound of the cyclic phenol sulfide that embodiment 1 is synthetic replaces to salicylic aluminium complex, after making toner according to method similarly to Example 5, and minute constant, saturated zone electric weight.The results are summarized in table 1.
[comparative example 3]
In order to compare, the zinc compound of the cyclic phenol sulfide that embodiment 1 is synthetic replaces to calixarene compound, after making toner according to method similarly to Example 5, and minute constant, saturated zone electric weight.The results are summarized in table 1.
Embodiment 9
1 part of the zinc compound of the cyclic phenol sulfide that 94 parts of cinnamic acrylic ester analog copolymer resins (CPR-100 processed of Mitsui Chemicals, Inc), embodiment 1 is synthetic, the heating and mixing device melting mixing of 110 ℃ of 5 parts of use of carbon black (MA-100 processed of Mitsubishi chemical Co., Ltd) are carried out coarse crushing with cooling potpourri with hammer-mill.After carrying out Crushing of Ultrafine with jet mill again, classification obtains the black toner of mean grain size 10 ± 0.5 μ m of dimension criteria.The ratio mixing that the ferrite carrier (Powdertech F96-150 processed of Co., Ltd.) that coats according to 4 parts of this toners, silicon is 100 parts, vibration, after making toner electronegative, measure time constant, the saturated zone electric weight that represents electric rising with Blow-off body of powder electrification amount determining device under the environment of 25 ℃ of temperature, humidity 50%.The results are summarized in table 1.
[comparative example C]
In order to compare, the zinc compound of the cyclic phenol sulfide that embodiment 1 is synthetic replaces to 4 times of bodies of above-mentioned ring-type that embodiment 1 obtains (in general formula (1), R is that the tert-butyl group, m are 4, n is 0, Y be all 4 times of bodies of ring-type of hydrogen atom), after making toner according to method similarly to Example 9, minute constant, saturated zone electric weight.The results are summarized in table 1.
[Comparative Example D]
In order to compare, the zinc compound of the cyclic phenol sulfide that embodiment 1 is synthetic replaces to 4 times of bodies of ring-type (in general formula (1), R is that the tert-butyl group, m are 4, n is 2, Y be all 4 times of bodies of oxidized cyclic of hydrogen atom) of the above-mentioned oxidized form that embodiment 3 obtains, after making toner according to method similarly to Example 9, minute constant, saturated zone electric weight.The results are summarized in table 1.
Embodiment 10
The zinc compound of the cyclic phenol sulfide that embodiment 1 is synthetic replaces to the cobalt compound of the synthetic cyclic phenol sulfide of embodiment 2, after making toner according to method similarly to Example 9, and minute constant, saturated zone electric weight.The results are summarized in table 1.
Embodiment 11
The zinc compound of the cyclic phenol sulfide that embodiment 1 is synthetic replaces to the iron compound of the synthetic oxidized cyclic phenol sulfide of embodiment 3, after making toner according to method similarly to Example 9, and minute constant, saturated zone electric weight.The results are summarized in table 1.
Embodiment 12
The zinc compound of the cyclic phenol sulfide that embodiment 1 is synthetic replaces to the calcium compound of the synthetic oxidized cyclic phenol sulfide of embodiment 4, after making toner according to method similarly to Example 9, and minute constant, saturated zone electric weight.The results are summarized in table 1.
[comparative example 4]
In order to compare, the zinc compound of the cyclic phenol sulfide that embodiment 1 is synthetic replaces to salicylic zinc complex, after making toner according to method similarly to Example 9, and minute constant, saturated zone electric weight.The results are summarized in table 1.
[comparative example 5]
In order to compare, the zinc compound of the cyclic phenol sulfide that embodiment 1 is synthetic replaces to salicylic aluminium complex, after making toner according to method similarly to Example 9, and minute constant, saturated zone electric weight.
The results are summarized in table 1.
[comparative example 6]
In order to compare, the zinc compound of the cyclic phenol sulfide that embodiment 1 is synthetic replaces to calixarene compound, after making toner according to method similarly to Example 9, and minute constant, saturated zone electric weight.
The results are summarized in table 1.
Figure 576901DEST_PATH_IMAGE004
By above content as can be known, the metallic compound of cyclic phenol sulfide of the present invention has good chargeding performance, the charge control agent that contains this compound has the good charged effect of giving, and the electronegative property toner that contains this charge control agent has highly charged performance.
If particularly respectively the Y in all use formulas of these comparative examples of Comparative examples A, B, C and D(shown in comparison sheet 1 is all the compound of hydrogen atom) and embodiment 5,7,9 and these embodiment of 11(all use the part of the Y in formula to be the compound of metallic atom) performance as can be known, because a part that makes Y becomes metallic atom, it is large that the saturated zone electric weight becomes, and time constant diminishes (it is better that the less electricity of time constant rises), and charge control agent of the present invention is more suitable for the high speed of printer in recent years.
Industrial applicibility
The metallic compound of cyclic phenol sulfide of the present invention has good chargeding performance, and the charge control agent with this compound was compared with former charge control agent, had highly charged performance.In addition, can provide and to adapt to the novel toner of the high speed of printer in recent years.And, the compound of colourless (white) is also arranged in the metallic compound of cyclic phenol sulfide of the present invention, as color toner with being also useful.

Claims (12)

1. a charge control agent, is characterized in that, contains the metallic compound of cyclic phenol sulfide of following general formula (1) expression as effective constituent:
Figure FFW00000077813800011
In formula, R represents the straight chain shape of carbon number 1 to 6 or the alkyl of a chain, and Y represents hydrogen atom or metallic atom, and m represents 4 to 9 integer, and n represents 0 or 2 integer, and wherein, in a plurality of Y, at least 1 is metallic atom, and described metal is transition metal or earth alkali metal.
2. charge control agent as claimed in claim 1 contains the metallic compound of the cyclic phenol sulfide of general formula (1) expression, and wherein m is 4.
3. charge control agent as claimed in claim 1 contains the metallic compound of the cyclic phenol sulfide of general formula (1) expression, and wherein m is 6.
4. charge control agent as claimed in claim 1 contains the metallic compound of the cyclic phenol sulfide of general formula (1) expression, and wherein m is 8.
5. charge control agent as described in any one in claim 2～4 contains the metallic compound of the cyclic phenol sulfide of general formula (1) expression, and wherein n is 0.
6. charge control agent as described in any one in claim 2～4 contains the metallic compound of the cyclic phenol sulfide of general formula (1) expression, and wherein n is 2.
7. a toner, is characterized in that, contain in the metallic compound of cyclic phenol sulfide of general formula claimed in claim 1 (1) expression more than a kind and colorant and binding resin.
8. toner, it is characterized in that, contain in the metallic compound of cyclic phenol sulfide more than a kind and colorant and binding resin, the metallic compound of described cyclic phenol sulfide is the metallic compound of the cyclic phenol sulfide of general formula claimed in claim 1 (1) expression, and m is 4.
9. toner, it is characterized in that, contain in the metallic compound of cyclic phenol sulfide more than a kind and colorant and binding resin, the metallic compound of described cyclic phenol sulfide is the metallic compound of the cyclic phenol sulfide of general formula claimed in claim 1 (1) expression, and m is 6.
10. toner, it is characterized in that, contain in the metallic compound of cyclic phenol sulfide more than a kind and colorant and binding resin, the metallic compound of described cyclic phenol sulfide is the metallic compound of the cyclic phenol sulfide of general formula claimed in claim 1 (1) expression, and m is 8.
11. toner, it is characterized in that, contain in the metallic compound of cyclic phenol sulfide more than a kind and colorant and binding resin, the metallic compound of described cyclic phenol sulfide is the metallic compound of the cyclic phenol sulfide of general formula claimed in claim 1 (1) expression, and n is 0.
12. toner, it is characterized in that, contain in the metallic compound of cyclic phenol sulfide more than a kind and colorant and binding resin, the metallic compound of described cyclic phenol sulfide is the metallic compound of the cyclic phenol sulfide of general formula claimed in claim 1 (1) expression, and n is 2.
CN200980126718.2A 2008-05-09 2009-05-08 Charge controlling agent and toner using metal compound of cyclic phenol sulfide Expired - Fee Related CN102089717B (en)

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JPWO2009136634A1 (en) 2011-09-08
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